Process of treating products containing vanadium, molybdenum, titanium, and tungsten.



Patented April 18, 1905.

. NME STATES PATENT OFFI E.

HENRI LOUIS HERRENSOHMI-DT, or LE GENEST, FRANCE.

PROCESS OF TREATING PRODUCTS CONTAINING VANADIUM, MOL YBDENUM, TITANIUM, AND' TUNGSTEN.

SPECIFICATION f ming p of Iletters Patent No. 787,758, dated April 18, 1905. Applicationfiled August 13, 1903. Serial No. 169,378.

To all whom it may concern:

Be it known that I, HENRI LOUIS HERREN- SCHMIDT, metallurgical engineer, of Le Genest, Mayenne, Republic of France, have invented a Process forthe Treatment of Ores or Products Containing Vanadium, Molybdenum, Titanium, or Tungsten, of which the following is a full, clear, and exact description. j

This invention relates to a process oftreating ores or products containing vanadium for the-purpose of obtainingvanadic acid or the vanadateof any metal, as well as alloys of vanadium with certain n1etals.such as nickel,

iron, copper, &c. '.in definite proportions.

The process is alsoequally applicable for the treatment of, ores or products containing v molybdenum, titanium, or tungsten.

The process which is hereinafter describedas applied to the treatment of ores or products containing vanadiumis characterized, essentially, by the following operations: first, the refining of a vanadate-of-sodaliquor obtained by treating the vanadium ore-or product with a soda salt, either by evaporation and crystallization or by the addition of vanadic acid,

"(which latter may result from a fractional precipitation obtained by the addition of vana-- 3 v tation of the vanadiumcontained in this puridium sulfate, which may be impure,) 'or of an fiedliqhor, either by means of the sulfate,

chlorid, or other soluble salt of a metalsuch as iron, nickel, copper, &c. with the object of obtaining the van-adate ofsaid metal, (vau'a date of iron, of nickel, of copper, &c.,) or by the action of concentrated sulfuric acid upon the liquor previously concentrated to a syrupy condition, with the object of obtaining vanadic acid; third, the reduction of oxygenated:

compounds of vanadium, which consists in re-Y ducing the vanadate of nickel, iron, copper, &c., by carbon, tar, or. other reducing agent with the object of obtaining the alloy desired.

In order that the invention may be more readily understood, I will proceed to describe the application of .the process to the'treatment of a vanadiferous lead ore of about the following composition, viz lead, iron, vanadium, silica, alumina, and copper.

The ore is fused with an alkaline carbonate,

latter case previously concentrated.

(carbonate of soda, for example',) as a flux and fuel. Metallic lead then' forms a cupreous matte, if the ore contains copper,'anda slag chiefly composed of Vanadate of soda and containing silica, alumina, and iron. is then either ground and washed or run direct into the water, preferably at aboiling temperature, to facilitate disintegration. The major the mother-liquors, or vanadic acid may be added to the liquor, causing the precipitation of the silica and alumina. Instead of directly employing vanadicv acid I may add vanadate of soda or sulfate or chlorid of Vanadium to the liquor, or a fractional precipitation may be effected by means of a metallic salt or by the addition of an acid to the liquor, in this The vanadium contained in thesolution of ,vanadate of sodapurified in the manner described is precipitated either by means of sul- .furic acid, if it be desired to obtain vanadic acid, or by a soluble salt of the metals from 'which a vanadate is to be obtained.

In treating vanadate of soda with sulfuric acid to obtain vanadic acid care should be taken to previously concentrate the vanadateof-soda liquor to a syrupy-consistency, If it be desired to obtain an alloysay, for example, vanadium-nickelthe .vanadium contained in the alkaline vanadate is precipitated by a soluble salt of nickel-sulfate "of nickel, for examplethis operation being preferably performed in the cold, in which case it will be complete. The precipitate of vanadium and nickel is then washed, dried, and calcined, the product constituting a material suited for making vanadium-nickel either in the electric furnace or by alumino-thermy, or, preferably, by a special reduction process, hereinafter described, which constitutes one ,of,

This slag.

I such as carbon, tar, &c.the mixture being subsequently agglomerated and heated.

Oxid of vanadium by itself is incapable of being reduced to pure metallic vanadium;but when it is in the presence of the oXid of another metal the reduction of the latter metal brings about that of the vanadium. There f is thus formed a carburized vanadium-nickel,

which may be dccarburized by any known process.

An alloy of nickel (iron, copper) and vanadium may also be obtained by intimately mixing oxid of nickel (iron, copper) with vanadic acid and reducing the mixture, as hereinbefore described, by the addition of a reducing agent, such as carbon, tar, &c.

Ithas been before stated that at an early stage of the process a slag was obtained containing an insoluble product composed of silica, iron, alumina, and a little vanadium. ble product if treated with concentrated sulfuric acid yields a solutioncontaining sulfate of vanadium, sulfate of alumina, sulfate of iron, while the greater part of the silica and alumina remains insoluble. This liquor is treated with soda to form impure vanadate of soda, which is treated in the same manner as the vanadate-of-soda liquor resulting from the dissolution of the slag obtained at an early stage of the process, or it is employed for efiecting the fractional precipitation intended for purifying the impurevanadate of soda, as before described.

-In the case of ores such as Colorado sand stones the ore in a finely-crushed-condition is-first attacked either' with soda or with sulfuric acid. The liquor obtained, containing If instead of vanadium-nickel it be This insolucontaining vanadium for the purpose of ob-.

taining vanadic acid, the same being characterized by the following operations, to wit:

(a) the refining of a vanadate-of-soda liquor by evaporation and crystallization; (b) the precipitation of the vanadium contained in the purified liquor by the action of concentrated sulfuric acid upon said liquor, previously concentrated to a syrupy condition; and (c) the-process of reduction by a reducing agent.

2. The herein-described process of treating ores containing vanadium, which consists in reducing the ore to a solution, refining the same and precipitating the vanadium contained in the liquid, and then reducing the vanadium salts or compound to an alloy.

3. The herein-described process of treating ores containing vanadium, which consists in reducing the ore to a solution, refining such solution, concentrating the same to a syrupy state, and precipitating the vanadium by means of a soluble salt or an acid, and then reducing the vanadium salts or compound to an alloy.

The foregoing specification of my process for the treatment of ores or products containing vanadium, molybdenum,

titanium, or tungsten signed by me this 27th day of July, 1903. 

